Methods and apparatuses for estimating on-wafer oxide layer reduction effectiveness via color sensing

ABSTRACT

Disclosed are methods of preparing a semiconductor substrate having a metal seed layer for a subsequent electroplating operation. In some embodiments, the methods may include contacting the surface of the semiconductor substrate with a plasma to treat the surface by reducing metal oxides thereon and thereafter measuring a post-plasma-contact color signal from said surface, the color signal having one or more color components. The methods may then further include estimating the extent of the oxide reduction due to the plasma treatment based on the post-plasma contact color signal. In some embodiments, estimating the extent of the oxide reduction due to the plasma treatment is done based on the b* component of the post-plasma contact color signal. Also disclosed are plasma treatment apparatuses which may implement the foregoing methods.

FIELD OF THE INVENTION

This disclosure relates to the fabrication of electronic devices, theelectroplating of semiconductor substrates, electroplating systems andapparatuses having integrated and/or in situ metrology systems forexamining semiconductor wafers during processing, and methods ofperforming metrology and examination of semiconductor wafers duringprocessing.

BACKGROUND

The fabrication of integrated circuits often involves one or more stepsof electroplating a layer of conductive metal onto the surface of asemiconductor wafer. For example, in some IC fabrication procedures, anelectroplating operation may be used to fill with metal the variousfeatures formed in the surface of a semiconductor wafer such as, forinstance, the trenches and vias used as conductive paths between variouscircuit elements. The electroplated metal is oftentimes copper, butdepending on the IC design, other metals may be appropriate and/oradvantageous including ruthenium, palladium, iridium, rhodium, osmium,cobalt, nickel, gold, silver, and aluminum. In some embodiments, alloysof these metals may be appropriate and/or advantageous.

In a typical electroplating operation, the surface of the wafer isexposed to an electroplating bath fluid which contains dissolved ions ofthe metal to be electroplated, and an electrical circuit is createdbetween an electrode in the bath (which serves as an anode) and surfaceof the wafer (which serves as the cathode). Flow of current through thiscircuit upon application of an applied voltage causes electrons to flowto the cathode surface and reduce dissolved metal ions in its vicinitythereby resulting in the plating out of solution of neutral elementalmetal onto the surface of the wafer.

However, for this circuit to be completed and for electrochemicalreduction of dissolved metal ions to occur, the surface of the wafer(serving as the circuit's cathode) must be, at least to a certainextent, relatively conductive. Accordingly, since the bare surface of asemiconductor wafer is not generally substantially conductive, theactual electroplating step in an electroplating operation is oftenpreceded by the deposition of a conductive seed layer which provides thenecessary conductive surface. Deposition of the seed layer may beaccomplished by any feasible method of depositing the seed material.Suitable methods may include, for example, physical vapor deposition(PVD), chemical vapor deposition (CVD), plasma-enhanced chemical vapordeposition (PECVD), conformal film deposition (CFD), atomic layerdeposition (ALD), and the like. Oftentimes, seed layer deposition andelectroplating is followed by an edge bevel removal (EBR) operation thatremoves seed metal deposited at the edge of the wafer where its presenceis not desired via the application of a thin viscous flow of etchantsolution over the wafer's edge.

However, oftentimes, after the seed layer is deposited, a wafer isremoved from vacuum and exposed to clean room ambient air. In someinstances, there could be a queue time ranging from a few minutes toseveral hours before the wafer is electroplated. Delay time andassociated exposure to ambient air can cause oxidation of the seedlayer—often referred to as “seed aging.” This oxide layer resulting fromseed aging, being substantially non-conductive, may act to reduceelectroplating efficiency or even prevent it from occurring. Inaddition, the surface wetting characteristics of the wafer may changealso contributing to defects on the wafer. Post-electroplating voids andpits have been seen on pattern wafers as a result of too muchpre-electroplating seed aging resulting in useless IC devices and thusnegatively impacting overall wafer yields. Moreover, it is observed thatseed aging effects are exacerbated in lower technology nodes—sub 22 nm,for example—where seed layers are generally very thin, for example, insome circumstances 50 Å or less. Seed dissolution and reduction incurrent density is also seen with thinner seed in localized spots deeperinto the vias and trenches with higher denser pattern densities, alsocausing post-electroplating wafer defects. Accordingly, methods andapparatuses have been developed to deal with oxide layer reductionand/or removal, and further improvements on these methods andapparatuses are disclosed herein.

SUMMARY OF THE DISCLOSURE

Disclosed herein are methods of preparing a semiconductor substratehaving a metal seed layer for a subsequent electroplating operation. Insome embodiments, the methods may include contacting the surface of thesemiconductor substrate with a plasma to treat the surface by reducingmetal oxides thereon and thereafter measuring a post-plasma-contactcolor signal from said surface, the color signal having one or morecolor components. The methods may then further include estimating theextent of the oxide reduction due to the plasma treatment based on thepost-plasma contact color signal. In some embodiments, estimating theextent of the oxide reduction due to the plasma treatment is done basedon the b* component of the post-plasma contact color signal.

Also disclosed herein are plasma treatment apparatuses for reducingmetal oxides present on the surface of a metal seed layer of asemiconductor substrate in preparation for a subsequent electroplatingoperation. In some embodiments, the apparatuses may include a processingchamber having at least one processing station therein, a substrateholder configured to hold a substrate at the processing station, aplasma generator configured to generate a plasma within and/or provideit to the processing chamber, and a color sensor configured to measure acolor signal from a substrate, the color signal having one or more colorcomponents. The apparatuses may further include a controller havingnon-transitory computer-readable instructions for operating theapparatus and its various components. In some embodiments, thecontroller may include instructions for operating the plasma generatorto generate a plasma within and/or provide it to the processing chamberso that the plasma contacts the surface of a substrate at the processingstation to treat it by reducing metal oxides thereon. In someembodiments, instructions may be included for operating the colorsensor, after the plasma contacts the substrate surface, to measure apost-plasma-contact color signal from the surface, the color signalhaving one or more color components. In some embodiments, instructionsmay be included for estimating the extent of the oxide reduction due tothe plasma treatment based on the post-plasma contact color signal. Insome embodiments, said color sensor of the apparatuses may be locatedand/or configured so as to measure the color signal from the substratewhile the substrate is located at the processing station. In someembodiments, the apparatuses may further include a load-lock configuredto provide substrate access to the processing chamber, and the colorsensor may be located and/or configured so as to measure the colorsignal from the substrate while the substrate is located within theload-lock.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A is a flowchart of a method of preparing a semiconductorsubstrate having a metal seed layer for a subsequent electroplatingoperation involving the measurement of at least one color signal.

FIG. 1B is a flowchart of another method of preparing a semiconductorsubstrate having a metal seed layer for a subsequent electroplatingoperation involving the measurement of at least two color signals.

FIG. 2 schematically illustrates a three color component color spaceusing “a*”, “b*”, and “L*” color components.

FIG. 3 presets a more detailed flowchart illustrating an electroplatingmethod including a plasma pretreatment and operations for estimating theextent of oxide reduction in the pretreatment akin to the operationsshown in FIGS. 1A and 1B.

FIG. 4 shows a cross-sectional schematic of an example of a plasmatreatment apparatus.

FIG. 5A schematically illustrates a multi-station plasma treatmentapparatus having 4 processing stations.

FIG. 5B presents a schematic of a load-lock of a plasma processingapparatus having a color sensor mounted in it.

FIG. 5C presents a vertical cross-section schematic (as indicated by thedashed line 505 in FIG. 5B) showing the positioning of the color sensorwithin the load-lock.

FIG. 5D presents a vertical cross-section schematic (zoomed in asindicated by the dashed ellipse 506 in FIG. 5C) showing the fiber optichead of the color sensor in detail.

FIG. 6A shows an exemplary flow diagram illustrating a method oftreating a substrate with a metal seed layer.

FIG. 6B shows an exemplary flow diagram illustrating another method oftreating a substrate with a metal seed layer.

FIGS. 7A-7D show examples of cross-sectional schematic diagramsillustrating various stages of treating a substrate with a metal seedlayer using a plasma treatment apparatus.

FIG. 8 shows the results of b* color component measurements done on 6wafers having 200 Å oxide layers before and after plasma pretreatment.

FIG. 9A shows the affect of H₂ plasma treatment on the L* colorcomponent.

FIG. 9B shows the affect of H₂ plasma treatment on the a* colorcomponent.

FIG. 9C shows the affect of H₂ plasma treatment on the b* colorcomponent.

FIG. 10A shows the value of the b* color component as a function of timeover the course of a “multilayer recipe” where the wafer passes throughan outbound load-lock twice.

FIG. 10B shows a close-up re-plotted view of a portion of the data fromFIG. 10A.

FIG. 11A plots values of the b* color component measured from 6 wafers(each having a 200 Å oxide layer) which have been plasma treated for 6different time durations at 250 C.

FIG. 11B plots values of the b* color component measured from 5 wafers(each having a 200 Å oxide layer) which have been plasma treated for 5different time durations at 75 C.

DETAILED DESCRIPTION

In the following disclosure, numerous specific embodiments are set forthin order to provide a thorough understanding of the inventive conceptsdisclosed herein. However, it will be appreciated by those skilled inthe art that the inventive concepts disclosed herein may in many casesbe practiced with or without certain of these specific details, such asby the substitution of alternative elements or steps, or the omission ofcertain elements or steps, while remaining within the scope and spiritof the inventive concepts disclosed herein. Furthermore, where certainprocesses, procedures, operations, steps, elements, modules, components,and/or systems are already well-known to those skilled in the art, theymay not be described herein in as great of detail as necessarilypossible, in order that the important aspects of the disclosed inventiveconcepts are not unnecessarily obscured.

Oxidation of the Seed Layer

Metal seed layers can readily react with oxygen or water vapor in theair and oxidize from a pure metal into a mixed film of a metal oxide anda buried pure metal. While the oxidation under ambient conditions may belimited to a thin surface layer of some metals, that thin layer mayrepresent a significant fraction or perhaps the entire thickness of thinseed layers used in current technology nodes. Relatively thin seedlayers may be necessitated by the technology node, such as the 4×nmnode, the 3×nm node, the 2×nm node, and the 1×nm node, and less than 10nm. The height to width aspect ratio of vias and trenches in technologynodes necessitating relatively thin metal layers can be about 5:1 orgreater. In such technology nodes, the average thickness of the metalseed layer can be less than about 100 Å as a result. In someimplementations, the average thickness of the metal seed layer can beless than about 50 Å.

Through the general chemical reactions shown in Equation 1 and Equation2 below, metals used for seed or barrier layers are converted to metaloxides (Mox), though the exact reaction mechanisms between the metalsurfaces (M) and ambient oxygen or water vapor can vary depending on theproperties and the oxidation state.

2M_((s))+O_(2(g))→2MOx _((s))  Equation 1

2M_((s))+H₂O_((g))→M₂Ox+H_(2(g))  Equation 2

For example, copper seed deposited on substrates is known to rapidlyform copper oxide upon exposure to the air. A copper oxide film can forma layer that is approximately 20 Å and upwards to 50 Å thick on top ofunderlying copper metal. As metal seed layers become thinner andthinner, the formation of metal oxides from oxidation in ambientconditions can pose significant technical challenges.

As mentioned, conversion of pure metal seed to metal oxide can beproblematic. This is true not only in current copper damasceneprocessing, but also for electrodeposition processes that use otherconductive metals, such as ruthenium, cobalt, silver, aluminum, andalloys of these metals. First, an oxidized surface is difficult to plateon. For one thing, the oxidized surface is not as conductive as the bareseed metal tending to inhibit the rate of electroplating. The surfacemay not be uniformly oxidized, however, making plating—since the rate ofplating depends on the surface conductivity—non-uniform as well as slow.Moreover, electroplating bath additives may interactive differently withmetal oxide versus pure metal, causing further non-uniformity in theelectroplating rate.

Second, as result of oxidation, voids may be formed in the metal seedlayer that may make portions of the seed layer unavailable to supportplating. The voids may form as a result of dissolution of metal oxideduring exposure to corrosive plating solutions. The voids also may formon the surface due to non-uniform plating. Additionally, plating bulkmetal on top of an oxidized surface can lead to adhesion or delaminationproblems, which can further lead to voids following subsequentprocessing steps, such as chemical mechanical planarization (CMP). Voidsthat result from etching, non-uniform plating, delamination, or otherprocesses may make the metal seed layer discontinuous, and unavailableto support plating. In fact, because modern damascene metal seed layersare relatively thin, such as (as stated) about 50 Å or thinner, even alittle oxidation may consume the entire thickness of the seed layer.

Third, and more generally, metal oxide formation has sometimes been seento cause issues with other substrate processing operations subsequent toelectroplating. For instance, it has sometimes been observed that metaloxide formation impedes the deposition of post-electrodeposition cappinglayers. In some situations, this may be due to the metal oxide layereffectively limiting the adhesion if the capping layer.

It may be difficult to avoid metal oxide formation on the seed layerafter it has been deposited but prior to the bulk electroplatingoperation. Various intervening processing steps may occur that exposethe seed layer to oxygen or water vapor in ambient conditions. Forexample, a PVD method of deposition a metal seed layer may be followedby one or more steps of rinsing (with de-ionized water, for example) andthen subsequent drying which is done prior to the bulk electrodepositionoperation. The rinsing step may be limited to a time, for example, ofbetween about 1 and 10 seconds, but may take a longer or shorter time.The subsequent drying may be between about 20 and 40 seconds, though thedrying step may take a longer or shorter time. During these steps, themetal seed layer may be exposed to ambient conditions and oxidation ofthe seed layer may take place.

Even in the absence of a particular intervening step (like rinsing anddrying) seed layer deposition, for example via PVD, is typically done ina different processing chamber than the electroplating cell used forelectrodeposition. As such, there is oftentimes and intervening vacuumbreak and transfer of the wafer between these processing modules duringwhich the seed layer may be exposed to ambient conditions, again,potentially resulting in seed layer oxidation. In some circumstances,the duration of this exposure may be anywhere between about 1 minute and4 hours, or more particularly between about 15 minutes and 1 hour. Notethat various suitable electro-plating/deposition/fill methods andapparatuses are described in U.S. Pat. No. 6,793,796, filed Feb. 28,2001 (attorney docket no. NOVLP073), which is hereby incorporated byreference in its entirety for all purposes. (The reference describes atleast four phases of the electro-plating/deposition/fill process anddiscloses controlled current density methods for each phase for optimalfilling of relatively small embedded features.)

Plasma Treatment to Remedy Oxidation of the Seed Layer

Due to the various factors that may result in metal seed layer oxidationin the intervening period between the seed layer's deposition andsubsequent bulk electroplating, an effective prescription for reducingmetal oxides post-seed layer deposition is highly desired. One approachis to pretreat (prior to bulk electroplating) the surface of thesubstrate by contacting it with a plasma which includes a reducing agentwhich thereby works to reduce the metal oxides formed on the substrate'ssurface. The reducing plasma used in this plasma pretreatment may beformed in the reaction chamber itself (the vacuum chamber holding thesubstrate for pretreatment), or the source of the plasma may be remotefrom the processing chamber—i.e., a “remote plasma” is formed andintroduced into the processing chamber to contact and treat thesubstrate surface—though perhaps also subject to subsequent modificationonce it enters the reaction chamber (e.g., ion filtering so thatradicals primarily contact the substrate, etc.).

Such methods and apparatuses for performing such an electroplatingpre-treatment with a reducing plasma are described in detail in U.S.patent application Ser. No. 14/086,770 (the “'770 application”), filedNov. 21, 2013, and titled “METHOD AND APPARATUS FOR REMOTE PLASMATREATMENT FOR REDUCING METAL OXIDES ON A METAL SEED LAYER,” nowpublished as US Pat. Pub. No. 2014/0256128, which is hereby incorporatedby reference in its entirety for all purposes. As disclosed in the '770application, depending on the embodiment the reducing gas species usedto form the reducing plasma may be hydrogen (H₂), ammonia (NH₃), carbonmonoxide (CO), diborane (B₂H₆), sulfite compounds, carbon and/orhydrocarbons, phosphites, and/or hydrazine (N₂H₄), and likewise, theenergized reducing species in the plasma may be ions of the reducing gasor radicals such as H*, NH₂*, or N₂H₃*.

Equation 3 shows an example of a reducing gas species such as hydrogengas being broken down into hydrogen radicals. Equation 4 shows thehydrogen radicals reacting with the metal oxide surface to convert themetal oxide to metal. For hydrogen gas molecules that are not brokendown or hydrogen radicals that recombine to form hydrogen gas molecules,the hydrogen gas molecules can still serve as a reducing agent forconverting the metal oxide to metal, as shown in Equation 5.

H₂→2H*  Equation 3

(x)2H*+MOx→M+(x)H₂O  Equation 4

(x)H₂+MOx→M+(x)H₂O  Equation 5

As mentioned, in some embodiments the pretreatment plasma may alsoinclude ions and other charged species of the reducing gas species,though it is often advantageous to filter out these charged species sothey do not reach the substrate and potentially damage the seed layer asdescribed in greater detail below.

Qualifying/Quantifying Plasma Pretreatment Performance

The foregoing plasma pretreatment has been found to be very effective atreducing the impact of seed aging on subsequent bulk electroplating.However, qualifying plasma pretreatment process performance in the fieldhas been found to be extremely challenging. To qualify pretreatmentperformance, typically a wafer is oxidized in a controlled environmentand then exposed to the oxide reducing plasma in a pretreatment module.Pre and post plasma treatment sheet resistance measurements are done andsheet resistance drop typically characterizes the performance of theplasma pretreatment. Even though this technique is useful in that, to acertain extent, it reveals the change pre and post plasma pretreatment,it is nevertheless plagued with many problems in the field. Since thesheet resistance measurements are done offline, there is a queue timebetween the plasma pretreatment and the offline measurements (which aredone at a separate, dedicated metrology tool). Due to the queue time,the performance of the pretreatment (e.g., the extent of oxide removal)tends to systematically be underestimated. More significantly, randomdifferences in queue time can be a false indication of pretreatmentperformance variability in the field. In some instances, if queue timesafter pretreatment are long enough, a pretreated wafer can regrow almostall the original oxide layer back before sheet resistance measurement isdone. Thus, such offline ex situ techniques are not ideal for qualifying(and quantifying) performance of plasma pretreatment in the field wherequeue time between pretreatment and measurement cannot be tightlycontrolled and/or even predicted. What is desired (and disclosed herein)are online in situ measurement techniques for quantifying oxide layerthickness in real-time—during or immediately after plasmapretreatment—thus providing for a reliable characterization of plasmapretreatment performance. Plasma pretreatment modules implementing suchtechniques are desired (and disclosed herein) as well.

Estimating On-Wafer Oxide Layer Removal Effectiveness Via Color Sensing

One mechanism for evaluating the effectiveness of oxide layer removal isto estimate oxide layer thickness using a color sensor after and/or evenduring the plasma pretreatment operation. It has been discovered thatcolor signal analysis measured from the wafer surface may be used as abasis of probing the thickness of any remaining oxide layer during orafter plasma pretreatment. In some embodiments, color signal measurementand analysis may accurately evaluate the performance of a plasmapretreatment module, of example, detecting issues with the module asthey arise and helping to prevent wafer scraps in the field. Thus,electroplating pretreatment methods which prepare a substrate forsubsequent electroplating may include reducing metal oxides on thesubstrate's surface by contacting the surface with a plasma, and thenmeasuring a color signal (from said surface), and estimating the extentof the oxide reduction (due to the plasma treatment) based on the colorsignal.

Such a method of preparing a semiconductor substrate having a metal seedlayer for a subsequent electroplating operation is illustrated by theflowchart in FIG. 1A. As shown in the figure, such a method 100 beginswith an operation 120 of contacting the surface of the semiconductorsubstrate with a plasma to treat the surface by reducing metal oxidesthereon. Then, after contacting with the plasma, in operation 130, apost-plasma-contact color signal is measured from said surface. Such acolor signal may have one or more color components as described furtherbelow. One or more of the color components may provide an indication ofthe thickness of the oxide layer. Thus, in operation 140, the measuredpost-plasma contact color signal is used as a basis for estimating theextent of the oxide reduction due to the plasma treatment.

Note that a color signal measured from the substrate surface typicallyhas multiple color components (though it could have just one colorcomponent). Once a color sensor has been tuned and it's setup optimized,it can detect small color changes on the surface of the wafer. In someembodiments, a color sensor outputs a color signal consisting of threecolor components. These could be RGB (red/green/blue) color values, butcolor components defining something other than an RGB color space arealso feasible.

For example, in some embodiments, the set of L*, and b* color componentsare measured and output by a color sensor; and these L*, a*, b* colorcomponents define an L*/a*/b* color space, as schematically illustratedin FIG. 2. As shown in FIG. 2, the “a*” color component indicates therelative proportion of green to red in the color signal, the “b*” colorcomponent indicates the relative proportion of blue to yellow in thecolor signal, and the “L*” color component is indicative of the overallluminosity or brightness of the color signal. Of course, while a valueof (a*,b*,L*) designates a position in this particular color space, oneof ordinary skill in the art will recognize that other representationsof color space are also feasible, and that the actual physical colordesignated by a particular (a*,b*,L*) triplet in this color space willbe potentially designated by a different triplet value of colorcomponents in a different color space. Moreover, one of ordinary skillin the art will readily appreciate that the inventive concepts disclosedherein are not restricted to this particular representation of colorspace in terms of a*, b*, and L* components.

It is also feasible in principle to use more than three colorcomponents, such as 4, 5, 6, 7, 8, 9, 10, or 16 color components in themeasurements and analysis, or a number of color components in a rangespanning 8 to 16 color components, or 16 to 32 color components, or 32to 64 color components, or 64 to 128 color components, or 128 to 256color components. If 3 or less color components are used, these colorcomponents may be chosen to be any combination of the *a, *b, or *Lcolor components illustrated schematically in FIG. 2, or a combinationof other types of color components (whether one, two, three) such as,for example, RGB (red, green, blue) color components. It should also benoted that although it is generally the case that the probe andreference color signals would include the same type and number of colorcomponents, it is not necessarily required. A metric indicative of thedifference between the two color signals (or between a measured signaland a vector average) having different numbers of color components couldstill be computed by ignoring the extra color components, for example.In yet other embodiments, the components of the probe color signal mayrepresent different color space components than the components of theone or more reference color signals. If this is the case, various colorspace vector projection methods may be used to still formulate ameaningful comparison metric. Finally, it should also be noted that adevice which senses colors and forms a color image—i.e., a colorcamera—may also, in principle, be used within the context of thisdisclosure. (Although, it is oftentimes the case that commerciallyavailable color cameras are not as sensitive to slight color differencesas commercially available color sensors. Yet, in principle, a colorcamera may also be effective, depending on the embodiment and thedesired sensitivity.)

With respect to this L*/a*/b* color space, it has been discovered thatthe b* color component is very effective upon which to base adetermination of the extent of oxide reduction (and/or removal) duringor after a plasma pretreatment operation. Partially, this is due to thedifference in b* color values attributable to oxide versus bare metalseed, however (and without being limited to a particular theory), it isalso due to the relative insensitivity of the b* color component toother irrelevant artifacts, fluctuations, instability, etc. during thecolor measurement. Some of the fluctuations and instabilities duringcolor sensor measurements can be due to vibration, changes in lightintensity, change in the gap between sensor head and the wafer, angle ofthe sensor head with respect to the wafer, wafer wobbling, and ambientcondition changes including temperature, pressure, humidity, etc. Thecolor sensor can have its own internal light source, however, smallchanges in the ambient light can interfere with the internal lightsource. For instance, the L* color component has been found to be quitedependent on the ambient light and hence not suitable as an indicator ofthe wafer color change due to oxide formation. The other colorcomponent, the a* component, has been found to not vary significantlybetween oxide and bare metal seed.

Note that the b* color component is defined herein to be the colorcomponent (e.g., of a multi-component color signal) which has a valueindicative of the relative proportion of blue versus yellow in the colorsignal (as discussed above with respect to FIG. 2). There are manypossible sets of color components which may define the color spacemeasured by a particular color sensor. Some color sensor may onlymeasure a single color component which could possibly be a b* colorcomponent. Some color sensors may measure more than 3 color componentsone of which is the b* color component. Furthermore, there may be somevariation in what is measured and/or defined as the b* color component(the difference may be by design, or it may be due to unintentionalmanufacturing variation), even in sensor which measure 3 colorcomponents. Nevertheless, in any of these cases, if a measured colorcomponent is indicative of the proportion of blue versus yellow, it isencompassed herein by what is referred to as the b* color component.

In some embodiments, a color signal upon which determination of oxidereduction effectiveness is based is measured immediately after theplasma treatment finishes (or as soon afterwards as is practical). (Howsoon after may depend on the placement and/or mounting of the colorsensor relative to where the plasma pretreatment occurs, though the ideais that it be near enough so that the problems discussed above withrespect to the usual offline metrology are significantly reduced.)However, in other embodiments, the color signal upon which anoxide-removal-effectiveness determination is based may be measuredduring the plasma-based pretreatment oxide removal, or even at multipletimes over the course of the pretreatment.

Such measurements may be used for real-time trouble spotting in thepretreatment process, so that problems may be rectified as soon aspossible and minimize wafer loses. However, it is also noted thatreal-time oxide layer thickness measurement during pretreatment(particularly if done at various intervals over the course ofpretreatment) may be used as a basis for real-time adjustment of thepretreatment process itself (e.g., by adjusting plasma strength) or forendpoint determination (i.e., determining when it advisable to stop thepretreatment process because all (or sufficient) oxide has been reducedand/or removed.

In any event, a variety of processing analysis options are then possibleas far as what one does with this “post-plasma-contact color signal” inorder to gauge oxide removal effectiveness. For instance, in someembodiments, the post-plasma-contact color signal may be compared to oneor more reference color signals. If the reference color signals areindicative of particular levels of oxide thickness—e.g., they weremeasured from wafers of known oxide layer thickness—then comparing themeasured post-plasma-contact color signal with these reference signalsprovides an estimate of oxide layer thickness (and thus oxide removaleffectiveness).

In some embodiments, this comparison could entail identifying thereference color signal which is closest to the measured post-plasmacontact color signal (the “probe” signal) and determining the oxidelayer thickness to be that associated with this particular reference. Ifthe comparison is based on a single color component, such as b* (or asingle color band, say for example, 650 nm±some Δλ), then “closest”reference just means that whose value of that color component is leastdifferent than the probe signal. If the comparison is based on multiplecolor components, then the “closest” reference is that whose vector ofcolor components is the least different form the probe, i.e., it has thesmallest value of

${\Delta \; E} = \sqrt{\sum\limits_{i = 1}^{N}\left\{ {{c_{i}({probe})} - {c_{i}({reference})}} \right\}^{2}}$

where c_(i) is the i^(th) component of the probe (measuredpost-plasma-contact color signal) and reference color signals, and N isthe number of color signal components (as is readily understood by onehaving ordinary skill in the art).

Of course, a differencing metric consisting of a scaled version of themagnitude of this vector difference would work similarly (the scalingpossibly due to unit conversion, for example), as would variousmonotonic functions of the vector difference magnitude. One of ordinaryskill in the art will readily appreciate that the specific functionalform of the metric is not critical as long as it results in a valueindicative of the difference between the probe and the reference colorsignals. The mathematical function representing the comparison metriccould be implemented as an analytic function of the color signals, itcould be implemented in a look-up table, or it could potentially beimplemented using some other computational methodology (a mixture ofanalytic function evaluation and table look-up, for instance).

Since the b* color component has been determined to be quite probativeof oxide layer thickness, in preferred embodiments, the comparisonswould be done in terms of the b* components of the post-plasma-contactmeasured (probe) and reference color signals. Thus, an analysis based onthe b* color component may involve calculating a set of metrics each ofwhich is monotonically related to the absolute value of the differencebetween the b* component of the post-plasma-contact color signal and theb* component of a reference color signal (corresponding to an oxidelayer of known thickness).

In more complicated embodiments, the oxide layer thickness could bedetermined by interpolating between reference color signals(corresponding to known oxide layer thicknesses). In some embodiments,multiple sets of color signals measured from multiple sets of referencewafers having known oxide layer thicknesses may be used to develop afunctional relationship between color signal and oxide layer thickness,and this relationship may be used to estimate the oxide layer thicknessof the test wafer based on the color signal measured from its surface(and thereby the effectiveness of the plasma pretreatment procedure).This functional relationship between oxide layer thickness and colorsignal could be linear, or roughly linear, or nonlinear, depending onthe scenario. The functional relationship will never be exact, ofcourse, but a best fit functional relationship may be selected ordetermined from one or more trial functional forms fit to a given set ofdata (i.e. color signal measurements from reference wafers of knownoxide layer thicknesses). The best fit will presumably establish valuesfor one or more parameters associated with the functional form as isreadily appreciated by one having skill in the art (e.g., the slope andintercept of a line if the functional relationship is assumed to belinear). Of course, as will also be appreciated by one having ordinaryskill in the art, once a functional relationship between color signaland oxide thickness is determined (whether it be linear, non-linear,etc.), the function may be applied to a measured color signal viaanalytic function evaluation, look-up table, etc. to calculate anapproximate seed layer thickness.

Another set of color signal processing options may base the analysis ofpretreatment effectiveness on a comparison of one more color signalsmeasured post-plasma-contact against one or more color signals measuredbefore the plasma pretreatment. Such a method of preparing asemiconductor substrate having a metal seed layer for a subsequentelectroplating operation is illustrated by the flowchart in FIG. 1B. Asshown in the figure, such a method 105 begins with an operation 110 ofmeasuring, before contacting with the plasma, a pre-plasma-contact colorsignal from the surface of a semiconductor substrate. Operation 130follows where the surface of the substrate is contacted with a plasma totreat the surface by reducing metal oxides thereon. Then, as in method100 from FIG. 1A, after the plasma contact, a post-plasma-contact colorsignal is measured from said surface in operation 130. Estimation of theextent of oxide reduction due to the plasma treatment is then done inoperation 145, which then is done by comparing the pre- andpost-plasma-contact color signals.

As with the post-plasma-contact color signal (or signals), apre-plasma-contact color signal may have one or more color componentsand, in particular, may include a b* component. In some embodiments, apre-versus-post plasma contact color signal comparison may involve thecalculation a metric which is indicative of the difference between thepre- and post-plasma-contact color signals. More particularly, if the b*component is used as the basis of comparison, the metric may bemonotonically related to the absolute value of the difference betweenthe b* component of the pre- and post-plasma-contact color signals.

Color sensor measurements for evaluating plasma pretreatmenteffectiveness has been found workable in well-controlled vacuumenvironments (such as in the plasma processing chamber) as well as inambient environments (such as within a chamber's inbound and outboundload-locks, as described in greater detail below). It has been found,however, that color signal measurement does work best when the head ofthe color sensor is close to the wafer's surface—i.e., only a small gapbetween sensor and wafer (ad described further below). This leads to themost stable measurements with the best signal-to-noise ratio. Furtherdetails regarding placement/or and mounting of the color sensor withrespect to the plasma processing chamber are described in greater detailbelow.

Further Details Regarding Plasma Treatment of the Seed Layer

FIG. 3 presets a more detailed flowchart illustrating an electroplatingmethod which includes plasma pretreatment and operations for estimatingthe extent of oxide reduction in the pretreatment akin to the operationsshown in FIGS. 1A and 1B. The method 300 begins with operation 305 wherea metal seed layer (such as a thin copper layer) is deposited on asubstrate. This provides a substrate having the metal seed layer on aplating surface of the substrate. The substrate may have recesses havingheight to width aspect ratios of greater than about 3:1 or greater thanabout 5:1. At operation 310, the substrate is transferred (possiblyunder ambient conditions) to a processing chamber, say of a pretreatmentmodule. At operation 315, under vacuum or reduced pressure in theprocessing chamber, the substrate is contacted with a reducing plasma(having ions and/or radical species of a reducing gas species formed inthe processing chamber or remote from it as described above). (Theradical and ion species may drift freely toward the surface of thesubstrate; ions, in particular, may be accelerated by an applied voltagebias, for example between a showerhead and the substrateholder/pedestal.) This treatment results, at operation 320, with thereduction of oxides on the metal seed layer and the formation of anun-oxidized (or nearly so) metallic surface. In some embodiments, asindicated in the figure, what was oxidized metal becomes an integratedfilm on the metal seed layer.

After oxide reduction, the next two operations involve estimation of theextent of oxide reduction based on color signal measurement. Inparticular, in operation 322 a post-plasma contact color signal ismeasured from the surface of the substrate. Then, again similar to FIGS.1A and 1B, the extent of the oxide reduction (accomplished in operation320) is estimated in operation 323 based on analysis of the color signalmeasured in operation 322. The method then proceeds to operation 325where the substrate is transferred under ambient conditions or under ablanket of inert gas to the electroplating system (or electrolessplating system, other metal deposition system, or another pretreatmentapparatus). Though metal oxides in the metal seed layer have beensubstantially reduced by exposing the metal oxide surfaces to a reducinggas atmosphere, performing operation 325 may present an additionalchallenge of re-oxidation from exposure to the ambient environment. Insome embodiments, exposure to ambient conditions may be minimized usingtechniques such as shortening the duration of transfer or controllingthe atmosphere during transfer. Additionally or alternatively, thetransfer is conducted in a controlled environment that is less oxidizingthan ambient conditions. To control the atmosphere during transfer, forexample, the atmosphere may be substantially devoid of oxygen. Theenvironment may be substantially inert and/or be low pressure or vacuum.In some embodiments, the substrate may be transferred under a blanket ofinert gas. As discussed below, the transfer in operation 325 may occurfrom the plasma pretreatment chamber to an electroplating cell in thesame apparatus, or two apparatuses (plasma treatment and electroplating)which are somewhat separated, but are nevertheless connected andintegrated with one another so that the substrate pretreated withreducing plasma may be transferred to the electroplating cell withreduced, or minimal, or no exposure to conditions which would causeoxidation of its now substantially bare metal surface. In any event,once transferred at operation 325 in FIG. 3, the method concludes withoperation 330 wherein metal is finally electroplated on to the substratesurface, in particular, and in preferred embodiments, onto what is now abare, substantially un-oxidized metal seed layer on the substratesurface.

The pretreatment plasma may also generate and include UV radiation fromthe reducing gas species. In some embodiments UV photons may heat thesurface of the substrate to activate the metal oxide surface forsubsequent reduction, or in some cases, the UV photons may havesufficient energy to cause reduction of the metal oxide itself. Thus, insome embodiments, radicals or ions of the reducing gas species, UVradiation from (neutrals, ions, and/or radicals of) the reducing gasspecies, or the reducing gas species itself can reduce the metal oxide.

In addition, the activated (ions, radicals, etc.) reducing gas speciescan be combined with mixing gas species, such as relatively inert gasspecies. Examples of relatively inert gas species can include nitrogen(N₂), helium (He), neon (Ne), krypton (Kr), xenon (Xe), radon (Rn), andargon (Ar). The flow rate of the reducing gas species for forming thereducing plasma can vary depending on the size of the wafer forprocessing. For example, said flow rate may be between about 10 standardcubic centimeter per minute (sccm) and about 100,000 sccm for processinga single 450 mm wafer. Other wafer sizes can also apply. For example,the flow rate of the reducing gas species used to form the plasma may bebetween about 500 sccm and about 30,000 sccm for processing a single 300mm wafer.

Temperature and pressure also affect the reactivity of the reducingplasma, although the temperature is typically maintained below thatwhich produces agglomeration of the metal seed layer during exposure tothe reducing gas atmosphere. As disclosed in the '770 application,suitable temperatures and pressures may be as follows: The temperatureof the reducing chamber can be relatively high to permit thedissociation of reducing gas species into radicals. For example, thereducing chamber can be anywhere between about 10 and 500° C., such asbetween about 50 and 250° C. Higher temperatures may be used to speed upmetal oxide reduction reactions and shorten the duration of exposure tothe reducing gas atmosphere. In some embodiments, the reducing chambercan have a relatively low pressure to substantially remove any oxygenfrom the reducing gas atmosphere, as minimizing the presence of oxygenin the atmosphere can reduce the effects of re-oxidation. For example,the reducing chamber can be pumped down to a vacuum environment or areduced pressure of between about 0.1 Torr and about 50 Torr. Theincreased temperature and/or the reduced temperature can also increasereflow of metal atoms in the metal seed layer to create a more uniformand continuous metal seed layer.

In some embodiments, as described in the '770 application, substratetemperature may be controlled separately from pretreatment chambertemperature in order to avoid or reduce damage to the metal seed layer.Depending on the type of metal in the metal seed layer, the metal canbegin to agglomerate above a threshold temperature. The effects ofagglomeration is more pronounced in relatively thin seed layers,especially in seed layers having a thickness less than about 100 Å.Agglomeration includes any coalescing or beading of a continuous orsemi-continuous metal seed layer into beads, bumps, islands, or othermasses to form a discontinuous metal seed layer. This can cause themetal seed layer to peel away from the surface upon which it is disposedand can lead to increased voiding during plating. For example, thetemperature at which agglomeration begins to occur in copper is greaterthan about 100° C. Different agglomeration temperatures may beappropriate for different metals.

In some embodiments, the substrate can be maintained at a temperaturebetween about −10° C. and about 150° C. In copper seed layers, forexample, the substrate can be maintained at a temperature between about75° C. and about 100° C. In cobalt seed layers, the substrate can bemaintained at a temperature greater than about 100° C. Thus, a coolingsystem such as an actively cooled pedestal and/or gas flow coolingapparatus in the pretreatment chamber may be used to keep the local areaof the substrate at temperatures below the agglomeration temperature.Depending on the embodiment, heat transfer may occur via conduction,convection, radiation, or combinations thereof. In some embodiments, acooling fluid circulation loop may actively cool the substrate.Embodiments including cooling features are described in U.S. Pat. No.7,327,948 (attorney docket no. NOVLP127X1), issued Feb. 5, 2008; U.S.Pat. No. 7,941,039 (attorney docket no. NOVLP127X3), issued Jan. 5,2011; U.S. patent application Ser. No. 11/751,584 (attorney docket no.NOVLP127X2), filed May 21, 2007; U.S. patent application Ser. No.13/370,579 (attorney docket no. NOVLP127C1), filed Feb. 10, 2012; U.S.Pat. No. 8,137,465 (attorney docket no. NOVLP127), issued Mar. 20, 2012;U.S. patent application Ser. No. 11/129,266 (attorney docket no.NOVLP361), filed May 12, 2005; U.S. patent application Ser. No.11/546,189 (attorney docket no. NOVLP198), filed Oct. 10, 2006; and U.S.patent application Ser. No. 12/749,170 (attorney docket no. NOVLP361D1),filed Mar. 29, 2010; each of which is incorporated herein by referencein its entirety and for all purposes.

The duration of the plasma pretreatment may vary depending on the otherprocess parameters, as described in detail in the '770 application. Forexample, exposure duration may be shortened by increasing plasma power,temperature, etc. Depending on the embodiment, suitable durations may bebetween about 1 and 60 minutes. For example, for pretreatment of copperseed layers, the duration of the exposure may be between about 10 and300 seconds.

In addition, as described in the '770 application, plasma pretreatmentmay provide the additional benefit of causing a reflowing of the metalin the portion of the seed layer which has been reduced by thepretreatment back to its elemental (non-oxidized) state. This reflowprocess may work to reduce voids and gaps in the metal seed layer bymobilizing and redistributing the metal atoms which improves seedcoverage and/or smoothness, and thereby forms a more uniform andcontinuous metal seed layer. In some implementations, the metal in themetal seed layer may be reflowed as a result of exposure to one or moreof increased temperature, reduced pressure, exposure to UV radiationfrom a dedicated UV source, exposure to UV radiation generated by thereductive plasma, and/or exposure to radicals and/or ions in the plasma,which are thought (not being limited to a particular theory) to causethe metal atoms to enter a more excited state and thereby become moremobile. Furthermore, this reflowing may cause an integration of themetal reduced via the pretreatment (i.e., recovered from the metal oxidelayer) to for a film integrated with the portion of the metal seed layerwhich was never oxidized. This film may be substantially continuous andconformal over the contours metal seed layer with the underlying portionof the seed layer which was never oxidized. As such, this reclaimedmetal film resists delamination and the like, which is oftentimes seento occur when oxide are eliminated by other techniques.

Color Sensor-Equipped Plasma Treatment Apparatuses

Disclosed are plasma treatment apparatuses for reducing metal oxidespresent on the surface of a metal seed layer of a semiconductorsubstrate in preparation for a subsequent electroplating operation. Theapparatuses include a processing chamber having at least one processingstation therein, a substrate holder configured to hold a substrate atthe processing station, a plasma generator (configured to generate aplasma within and/or provide it to the processing chamber), and acontroller having non-transitory computer-readable instructions foroperating the apparatus. The controller's instructions may includeinstructions for operating the plasma generator to generate a plasmawithin the processing chamber. In some embodiments, the instructionscause the plasma to be generated remotely from the processing chamber(as described further below) and then provided to the processingchamber. In any event, execution of the plasma generating (and anyrelated) instructions result in the plasma contacting the surface of asubstrate at the processing station to treat it by reducing metal oxidesthereon. However, in addition to the foregoing features, the plasmatreatment apparatuses (electroplating pretreatment apparatuses)disclosed herein further include a color sensor for, in conjunction withthe controller, providing real-time in situ estimation (and in somecases, continuous monitoring) of the performance of the plasmapretreatment apparatuses.

Thus, the controller may execute instructions for substrate processingoperations analogous to those operations described above: Operating theplasma generator to generate a plasma within and/or provide it to theprocessing chamber so that the plasma contacts the surface of asubstrate at the processing station to treat it by reducing metal oxidesthereon; operating the color sensor, after the plasma contacts thesubstrate surface, to measure a post-plasma-contact color signal fromthe surface, the color signal having one or more color components;estimating the extent of the oxide reduction due to the plasma treatmentbased on the post-plasma contact color signal. Additional operationswhich may be performed by the controller include, but are not limitedto: providing the semiconductor substrate to the processing stationwithin the processing chamber, operating a remote plasma source in theplasma generation operation, controlling exposure of the substrate'soxidized metal seed layer to the plasma, etc.

The color sensor may be positioned/located/mounted at various positionswithin the plasma treatment apparatus. For instance, in someembodiments, the color sensor may be positioned/located/mounted withinthe plasma processing chamber itself so that the sensor may beconfigured to measure a color signal (or signals) from a substrate whilethe substrate is located at the processing station (within the chamber)for plasma treatment. In other embodiments, the color sensor may bepositioned/located/mounted within the apparatus's inbound or outboundload-locks (which provides substrate access to and from the plasmaprocessing chamber). In this sort of arrangement, a post-plasma-contactcolor signal (or signals) may be measured in situ by a color sensorlocated in the outbound load-lock, and thus provide an estimate ofplasma pretreatment effectiveness, albeit not in real-time during theplasma treatment. Additionally, however, if another color sensor ismounted in the inbound load-lock, a pre-plasma-contact color signal maybe measured, additionally, before the plasma treatment, and thus acomparison of pre and post plasma contact color signals provides abefore-and-after basis for evaluating oxide removal effectiveness.

The hardware assembly of the color sensor, in some embodiments, mayinclude a fiber optic sensor head and a sensor body; and the sensor bodymay contain a color signal processing module having computer-readableinstructions for processing color signals. Thus the foregoing discussionof color sensor positioning/mounting applies more precisely to the fiberoptic head of the color sensor. This is described further below inrelation to various figures. Before those details, first described arevarious other aspects of the plasma processing apparatus: Oneinteresting aspect is a showerhead feature of the plasma processingapparatus which is located between the plasma source and thesemiconductor substrate. In some embodiments, it is desired thatprimarily free-radicals in the plasma contact the substrate and reduceoxides thereon—as opposed to ions in the plasma—and the showerheadfeature described below may work to filter out plasma ions, so that onlyplasma free-radicals reach the surface of the substrate.

FIG. 4 shows a cross-sectional schematic of an example of a plasmatreatment apparatus. The plasma treatment apparatus 400 includes aprocessing chamber 450 which has a single substrate processingstation—as provided by substrate holder 405 (which may be a pedestal)for holding substrate 410. The plasma treatment apparatus 400 alsoincludes a plasma generator configured to generate a plasma. Here,remote plasma source 440 generates the plasma remotely and thereafterprovides it to the processing chamber through showerhead 430 (which islocated between the substrate 410 and the remote plasma source 440).However, in other embodiments, the plasma generator may generate theplasma from within the processing chamber itself.

A reducing gas species 420 can flow from the remote plasma source 440towards the substrate 410 through the showerhead 430. A remote plasmamay be generated in the remote plasma source 440 to produce radicals ofthe reducing gas species 420. The remote plasma may also produce ionsand other charged species of the reducing gas species. For example,coils 444 may surround the walls of the remote plasma source 440 andgenerate a remote plasma in the remote plasma source 440.

The remote plasma may further generate photons, such as UV radiation,from the reducing gas species. In some implementations, the plasmatreatment apparatus can further include a UV source. The UV source caninclude UV broadband lamps such as mercury lamps, UV excimer lamps, UVexcimer lasers, and other appropriate UV sources. Aspects of the UVsource can be described in U.S. patent application Ser. No. 13/787,499(attorney docket no. LAMRP027), filed Mar. 6, 2013, which isincorporated herein by reference in its entirety and for all purposes.In some implementations, the reducing gas species can be exposed to UVradiation from the UV source to form radicals and other charged speciesof the reducing gas species, which can react with a metal oxide surfaceof a metal seed layer to reduce metal oxide.

In some embodiments, the coils 444 may be in electrical communicationwith a radio frequency (RF) power source or microwave power source. Anexample of a remote plasma source 440 with an RF power source can befound in the GAMMA®, manufactured by Lam Research Corporation ofFremont, Calif. Another example of an RF remote plasma source 440 can befound in the Astron®, manufactured by MKS Instruments of Wilmington,Mass., which can be operated at 440 kHz and can be provided as a subunitbolted onto a larger apparatus for processing one or more substrates inparallel. In some embodiments, a microwave plasma can be used with theremote plasma source 440, as found in the Astex®, also manufactured byMKS Instruments. A microwave plasma can be configured to operate at afrequency of 2.45 GHz.

In embodiments with an RF power source, the RF generator may be operatedat any suitable power to form a plasma of a desired composition ofradical species. Examples of suitable powers include, but are notlimited to, powers between about 0.5 kW and about 6 kW. Likewise, the RFgenerator may provide RF power of a suitable frequency, such as 13.56MHz for an inductively-coupled plasma.

Reducing gas species 420 are delivered from a gas inlet 442 and into aninternal volume of the remote plasma source 440. The power supplied tothe coils 444 can generate a remote plasma with the reducing gas species420 to form radicals of the reducing gas species 420. The radicalsformed in the remote plasma source 440 can be carried in the gas phasetowards the substrate 410 through the showerhead 430. An example of aremote plasma source 440 with such a configuration can be described inU.S. Pat. No. 8,084,339 (attorney docket no. NOVLP414), issued Dec. 27,2011, which is incorporated herein by reference in its entirety and forall purposes. The radicals of the reducing gas species 420 can reducemetal oxides on the surface of the substrate 410.

In addition to radicals of the reducing gas species, the remote plasmacan also generate and include ions and other charged species of thereducing gas species 420. In some embodiments, the remote plasma mayinclude neutral molecules of the reducing gas species 420. Some of theneutral molecules may be recombined molecules of charged species fromthe reducing gas species 420. The neutrals or recombined molecules ofthe reducing gas species 420 can also reduce metal oxides on the surfaceof the substrate 410, though they may take longer to react and reducethe metal oxides than the radicals of the reducing gas species 420. Theions may drift to the surface of the substrate 410 and reduce the metaloxides, or the ions may be accelerated toward the surface of thesubstrate 410 to reduce the metal oxides if the substrate support 405has an oppositely charged bias. Having species with higher ion energiescan allow deeper implantation into the metal seed layer to createmetastable radical species further from the surface of the substrate410. For example, if the substrate 410 has high aspect ratio features,such as between about 10:1 and about 60:1, ions with higher ionicenergies may penetrate deeper into such features to provide reduction ofthe metal oxide more throughout the features. In contrast, some of theradicals of the reducing gas species 420 from remote plasma generationmay recombine in the field or near the top of the features. The ionswith higher ionic energies (such as 10 eV-100 eV) can also be used tore-sputter and reflow the metal in the metal seed layer, which canresult in a more uniform seed coverage and reduce the aspect ratio forsubsequent plating or metal deposition (such as PVD, CVD, ALD).

In FIG. 4, the plasma treatment apparatus 400 may actively cool orotherwise control the temperature of the substrate 410. In someembodiments, it may be desirable to control the temperature of thesubstrate 410 to control the rate of the reduction reaction and theuniformity of exposure to the remote plasma during processing. It mayalso be desirable to control the temperature of the substrate 410 toreduce the effects of oxidation on the substrate 410 before, during,and/or after processing.

In some embodiments, the plasma treatment apparatus 400 can includemovable members 415, such as lift pins, that are capable of moving thesubstrate 410 away from or towards the substrate support 405. Themovable members 415 may contact the lower surface of the substrate 410or otherwise pick up the substrate 410 from the substrate support 405.In some embodiments, the movable members 415 may move the substrate 410vertically and control the spacing between the substrate 410 and thesubstrate support 405. In some embodiments, the movable members 415 caninclude two or more actuatable lift pins. The movable members 415 can beconfigured to extend between about 0 inches and about 5 inches, or more,away from the substrate support 405. The movable members 415 can extendthe substrate 410 away from a hot substrate support 405 and towards acool showerhead 430 to cool the substrate 410. The movable members 415can also retract to bring the substrate 410 towards a hot substratesupport 405 and away from a cool showerhead 430 to heat the substrate410. By positioning the substrate 410 via the movable members 415, thetemperature of the substrate 410 can be adjusted. When positioning thesubstrate 410, the showerhead 430 and the substrate support 405 can beheld at a constant temperature.

In some embodiments, the plasma treatment apparatus 400 can include ashowerhead 430 that allows for control of the showerhead temperature. Anexample of a showerhead configuration that permits temperature controlcan be described in U.S. Pat. No. 8,137,467 (attorney docket no.NOVLP246), issued Mar. 20, 2012, and U.S. Patent Publication No.2009/0095220 (attorney docket no. NOVLP246X1), published Apr. 16, 2009,both of which are incorporated herein by reference in their entirety andfor all purposes. Another example of a showerhead configuration thatpermits temperature control can be described in U.S. Patent PublicationNo. 2011/0146571 (attorney docket no. NOVLP329), published Jun. 23,2011, which is incorporated herein by reference in its entirety and forall purposes. To permit active cooling of the showerhead 430, a heatexchange fluid may be used, such as deionized water or a thermaltransfer liquid manufactured by the Dow Chemical Company in Midland,Mich. In some embodiments, the heat exchange fluid may flow throughfluid channels (not shown) in the showerhead 430. In addition, theshowerhead 430 may use a heat exchanger system (not shown), such as afluid heater/chiller to control temperature. In some embodiments, thetemperature of the showerhead 430 may be controlled to below about 30°C., such as between about 5° C. and about 20° C. The showerhead 430 maybe cooled to reduce damage to the metal seed layer that may result fromexcess heat during processing of the substrate 410. The showerhead 430may also be cooled to lower the temperature of the substrate 410, suchas before and after processing the substrate 410.

In some embodiments, the showerhead 430 may include a plurality ofholes. Increasing the size and number of holes in the showerhead 430and/or decreasing the thickness of the showerhead 430 may permit greaterflow of radicals, ions, and UV radiation from the reducing gas species420 through the showerhead 430. Exposing the metal seed layer to moreradicals, ions, and UV radiation can provide more UV exposure andenergetic species to reduce metal oxide in the metal seed layer. In someembodiments, the showerhead 430 can include between about 100 and about900 holes. In some embodiments, an average diameter of the holes can bebetween about 0.05 and about 0.5 inches. This can result in an open areain the showerhead 430 due to holes of between about 3.7% and about 25%.In some embodiments, the showerhead 430 can have a thickness betweenabout 0.25 and about 3.0 inches.

In some embodiments, the substrate support 405 may be configured to moveto and away from the showerhead 430. The substrate support 405 mayextend vertically to control the spacing between the substrate 410 andthe showerhead 430. When reducing metal oxides on the substrate 410, theuniformity as well as the rate of the reduction on the substrate 410 maybe tuned. For example, if the substrate support 405 is closer to theshowerhead 430, reduction of the metal oxide on the surface of thesubstrate 410 may proceed faster. However, the center of the substrate410 may get hotter than the edges of the substrate 410, which can resultin a less uniform reduction treatment. Accordingly, the spacing betweenthe substrate 410 and the showerhead 430 can be adjusted to obtain adesired rate and uniformity for processing the substrate 410. In someembodiments, the substrate support 405 can be configured to extendbetween about 0 inches and about 5 inches, or greater than about 5inches, from the showerhead 430.

In some embodiments, the temperature of the substrate support 405 mayalso be adjusted. In some embodiments, the substrate support 405 can bea pedestal with one or more fluid channels (not shown). The fluidchannels may circulate a heat transfer fluid within the pedestal toactively cool or actively heat the pedestal, depending on thetemperature of the heat transfer fluid. Embodiments that include suchfluid channels and heat transfer fluids can be described in activelycooled pedestal systems discussed earlier herein. The circulation of theheat transfer fluid through one or more fluid channels can control thetemperature of the substrate support 405. Temperature control of thesubstrate support 405 can control the temperature of the substrate 410to a finer degree. In some embodiments, the temperature of the substratesupport 405 can be adjusted to be between about 0° C. and about 400° C.

In some embodiments, the plasma treatment apparatus 400 can include oneor more gas inlets 422 to flow cooling gas 460 through the processingchamber 450. The one or more gas inlets 422 may be positioned above,below, and/or to the side of the substrate 410. Some of the one or moregas inlets 422 may be configured to flow cooling gas 460 in a directionthat is substantially perpendicular to the surface of the substrate 410.In some embodiments, at least one of the gas inlets 422 may delivercooling gas 460 through the showerhead 430 to the substrate 410. Some ofthe one or more gas inlets 422 may be parallel to the plane of thesubstrate 410, and may be configured to deliver a cross-flow of coolinggas 460 across the surface of the substrate 410. In some embodiments,the one or more gas inlets 422 may deliver cooling gas 460 above andbelow the substrate 410. The flow of cooling gas 460 across thesubstrate 410 can enable rapid cooling of the substrate 410. Rapidcooling of the substrate 410 can reduce the oxidation of the metal seedlayer in the substrate 410. Such cooling of the substrate 410 may takeplace before and after processing of the substrate 410. The flow rate ofthe cooling gas 460 for cooling can be between about 0.1 standard litersper minute (slm) and about 100 slm.

Examples of cooling gas 460 can include a relatively inert gas, such asnitrogen, helium, neon, krypton, xenon, radon, and argon. In someembodiments, the cooling gas 460 can include at least one of nitrogen,helium, and argon.

In some embodiments, the cooling gas 460 can be delivered at roomtemperature, such as between about 10° C. and about 30° C. In someembodiments, the cooling gas 460 can be delivered at a temperature lessthan room temperature. For example, a cold inert gas may be formed byexpanding a cold liquid to gas, such as liquid argon, helium, ornitrogen. Thus, the temperature range of the cooling gas 460 used forcooling can be broadened to be anywhere between about −270° C. and about30° C.

In some embodiments, the plasma treatment apparatus 400 may be part ofor integrated with an electroplating apparatus (not shown). Oxidation ofthe metal seed layer in the substrate 410 can occur rapidly duringexposure to ambient conditions. By attaching or otherwise connecting theplasma treatment apparatus 400 to the electroplating apparatus, theduration of exposure to ambient conditions of the substrate 410 can bereduced. For example, the transfer time between the plasma treatmentapparatus following treatment and the electroplating apparatus can bebetween about 15 seconds and about 90 seconds, or less than about 15seconds.

Table I summarizes exemplary ranges of process parameters that can beused with certain embodiments of a plasma treatment apparatus 400.

TABLE I Parameter Parameter Range Pedestal Temperature 0° C.-400° C.Showerhead Temperature 5° C.-30° C.  Pedestal Dropping Vertical Travel0″-5″ Lift Pins Raising Vertical Travel 0″-5″ Cooling Gas Flow 0.1-100slm (N₂/Ar/He - pure or mixture) Cooling Gas Temperature −270° C.-30°C.   Process Gas Flow 0.5 slm-30 slm (H₂/He/NH₃—pure or mixture) ProcessPressure 0.5-6 Torr Venting Gas Flow Nominally same as cooling gasVenting Gas Nominally same as cooling gas RF Plasma Power 0.5-6 kWPlasma treatment apparatus to 15-90 seconds Electroplating ApparatusTransfer Time Showerhead hole number 100-900 Showerhead thickness0.25″-3.0″ Showerhead hole diameter 0.05″-0.5″ Showerhead open area dueto 3.7%-25% holes

A controller 435 may contain instructions for controlling parameters forthe operation of the plasma treatment apparatus 400. The controller 435will typically include one or more memory devices and one or moreprocessors. The processor may include a CPU or computer, analog and/ordigital input/output connections, stepper motor controller boards, etc.The plasma treatment apparatus can be configured to perform a pluralityof operations that is not limited to treating a substrate with a remoteplasma. The plasma treatment apparatus can be configured to transfer(such as load/unload) a substrate efficiently to and from anelectroplating apparatus, electroless plating apparatus, or other metaldeposition apparatus. The plasma treatment apparatus can be configuredto efficiently control the temperature of the substrate by positioningthe substrate using movable members and/or the using substrate support.The plasma treatment apparatus can be configured to efficiently controlthe temperature of the substrate by controlling the temperature of thesubstrate support and the temperature of the showerhead. The plasmatreatment apparatus can be configured to tune the rate of reductionreaction and the uniformity of the reduction reaction by positioning thesubstrate support relative to the showerhead. The plasma treatmentapparatus can be configured to control the environmental conditionssurrounding the substrate by controlling the gases and flow rates of thegases delivered into the processing chamber. Such operations can improvethe processing of the substrate while also integrating additionaloperations into a single standalone apparatus. Thus, a single apparatuscan be used for treating and cooling the substrate, rather than usingtwo separate modules. Furthermore, by configuring the plasma treatmentapparatus to be able to perform some of the operations described above,the plasma treatment apparatus can reduce potential oxidation of themetal seed layer before, during, and after processing of the substrate.

FIG. 4 illustrate a plasma treatment apparatus having a singleprocessing station. However, plasma treatment apparatuses may havemultiple processing stations so that multiple substrates may beprocessed in parallel. Depending on the embodiment, one or more of theprocessing stations may have a color sensor positioned/mounted tomeasure color signal and to thus assess—oxide removal performance insitu and in real-time during the oxide removal process. FIG. 5Aschematically illustrates such a multi-station plasma treatmentapparatus 500 having 4 processing stations, 541-544. In this embodiment,a single processing chamber 510 defines a high-vacuum environment forall 4 stations, however, in certain scenarios, curtains of gas may beflowed between the different processing stations to volumetricallyisolate them from each other (at least to a certain extent).Furthermore, this embodiment employs a carousel 520 on which thesubstrates are positioned which may serve to rotate the substratesamongst the 4 processing stations. Thus, depending on the embodiment,the 4 processing stations may perform the same or different processingoperations. Moreover, even if the same processing operation (oroperations) are performed at each of the 4 stations, it may still beadvantageous to rotate semiconductor substrates through all 4 processingstations so that any systematic differences in processing are “averagedout” over the 4 stations.

Substrates enter the processing apparatus 500 through inbound load-lock531 and exit through outbound load-lock 532. With operation of theload-locks, entry and removal of semiconductor substrates from theapparatus may accomplished without breaking the high-pressure vacuumenvironment provided by processing chamber 520. Specifically, in theembodiment shown in the figure, this may this is done by closingload-lock seals 533 and 534 (which lead to the processing chamber),after placing substrates in the load-locks 531 and 532, and thereafteropening the load-lock doors 535 and 536 (which lead to the ambientenvironment outside the apparatus).

Within apparatus 500, substrates are transferred to and from the inboundand outbound load-locks 531 and 532 via wafer handler robot 540. Notethat in this embodiment, robot 540 only transfer wafers to theprocessing stations nearest to it, processing stations 541 and 542. Theother two processing stations 543 and 544 are accessed via rotation ofcarousel 520. Additional seals 561 and 562 may provide the wafer handlerrobot 540 access to processing chamber 510.

Color sensors may be positioned/mounted/located within plasma treatmentapparatus 500 in various locations. Illustrated in FIG. 5A, a colorsensor 595 is shown located at processing station 541. Rotation ofsubstrates amongst processing stations via the carousel may make itfeasible to have just a single color sensor in the processing chamber.FIG. 5A also shows apparatus 500 having color sensors 591 and 592located in the inbound and outbound load-locks, respectively. Asdescribed above, this provides the ability to measure color signalsbefore and after the plasma pretreatment process.

FIGS. 5B through 5D provide more detailed views of the mounting of acolor sensor in a load-lock. In particular, FIG. 5B shows a load-lock530 having a color sensor 596 and thus could correspond to outboundload-lock 532 in FIG. 5A. FIG. 5C shows a vertical cross-section asindicated by the dashed line 505 in FIG. 5B (as opposed to FIGS. 5A and5B which show the load-lock from above). The vertical cross-sectionshown in FIG. 5C shows the positioning of the color sensor, and moreparticular shows that this particular color sensor's hardware assemblyincludes a fiber optic sensor head 596A, coupled one or more fiber opticlines bundled together in a single cable housing 596B which terminatesin what can be referred to as color sensor body 596C (as mentionedabove) which holds the actual color detection electronics. In someembodiments, sensor body 596C may additionally contain a color signalprocessing module having logic and/or computer-readable instructions forprocessing color signals (transmitted from the fiber optic sensor head)beyond basic detection (e.g., calibration, contrast enhancement, etc.).It is to be noted, therefore, that the foregoing discussion of colorsensor positioning/mounting applies more precisely to the fiber optichead of the color sensor, rather than the entire color sensor. Anexample of such a color sensor for integration into a plasma treatmentapparatus which measures the three a*, b*, and L* color components asillustrated in FIG. 2 is the Micro-Epsilon model color sensormanufactured by Micro-Epsilon of Germany.

FIG. 5C illustrates that the color sensor 596, or more precisely thecolor sensor's fiber optic head 596A, is pointed at the edge of wafer507 within load-lock 530. It is noted that since the color sensor istrained on a region of the wafer other than it's center, in principle,rotation of the wafer may allow for multiple color signals to bemeasured at multiple azimuthally rotated points on the wafer surface.This may be more feasible when the sensor is mounted in the processingchamber instead of in the load-lock, depending on where a rotatablesubstrate holder may potentially be located. Multiple azimuthallydistributed color signal measurements are, of course, not required, butthey may provide for enhanced accuracy and precision by verifying oxideremoval performance around the entire wafer perimeter.

FIG. 5D presents another vertical cross-section, this time zoomed in onthe region indicated by the dashed ellipse 506 in FIG. 5C. Here, thefiber optic color sensor head 596A is shown in detail located withinmount 598 which sits in the upper wall of load-lock 530. A translucentquartz window 597 allows light reflected back up from the substrate 507(FIG. 5C) to reach color sensor 597 within it's mount 598.

In some embodiments, the color sensor may additionally include a lightsource for illuminating the substrate surface. This could also be by wayof fiber optics; in other words the one or more fiber optic linesbundled together in cable 596B may transmit light generated from sensorbody 596C to sensor head 596A where the light is emitted and directedtoward the substrate. Typically, substantially white light is used andtrained on a relatively small point on the substrate surface. With thesensor head positioned at 90 degrees relative to the substrate surfaceand in close proximity to it (as shown in FIG. 5C), the light reflectedis collected by sensor head 596A, and carried back via cable 596B to theactual electronic color detector located in the color sensor's body596C. Of course, whether the physical configuration of the color sensorincludes multiple physical units comprising a main body, cable housing,and fiber optic sensor head as schematically depicted in FIG. 5C, orwhether the color sensor is configured as a single physical unit, is notcritical to the operation and functioning of the inventive conceptsdisclosed herein.

In some embodiments, the one or more color sensors of a plasma treatmentapparatus are configured to send signals (electronically) to theapparatus's controller (e.g., controller 550 in FIG. 5). The controllermay be configured to receive the signals and process them, implementingany of the color signal analysis methodologies described herein forestimating the extent of oxide reduction post plasma treatment (orduring plasma treatment). However, in some embodiments a color signalprocessing module within the color sensor itself may have sufficientprocessing power to implement the methodologies disclosed herein toassess the extent of oxide reduction. In these sorts of embodiments, thecolor sensor may include logic for signaling the main apparatuscontroller when there is a detected problem with the plasma treatmentprocess.

FIG. 6A shows an exemplary flow diagram illustrating a method oftreating a substrate with a metal seed layer. FIGS. 7A-7D show examplesof cross-sectional schematic diagrams illustrating various stages oftreating a substrate with a metal seed layer using a plasma treatmentapparatus. Some of the steps discussed in FIG. 6A may be discussed withrespect to a corresponding cross-sectional schematic diagram in FIGS.7A-7D.

In FIG. 6A, the process 600 a can begin with step 605 a where asubstrate is provided in a processing chamber. The substrate can includea metal seed layer, where a portion of the metal seed layer has beenconverted to oxide of the metal. Prior to treatment of the substrate bya remote plasma, the substrate can be loaded into a processing chamberof a plasma treatment apparatus. In some embodiments, the substrate canbe provided on one or more movable members in an actuated position. Insome embodiments, inert gas may be flowed through the processing chamberto cool the substrate during loading. This can reduce additionaloxidation of the substrate during loading. In some embodiments, uponloading the substrate into the processing chamber, the processingchamber can be closed and pumped down to vacuum or to a reducedpressure. This can provide an environment that is substantially free ofoxygen. The pressure of the processing chamber can be between about 0.5Torr and about 6 Torr, such as between about 0.5 Torr and 3 Torr.Reduced pressures can reduce the presence of oxygen in the environment.Thus, loading the substrate into the processing chamber in suchconditions can reduce additional oxidation of the metal seed layer.

FIG. 7A shows an example of a cross-sectional schematic diagram of aplasma treatment apparatus 700 at one of the stages of treating asubstrate with a metal seed layer (such as at step 605 a). The plasmatreatment apparatus 700 includes a substrate support 705 in a processingchamber 750, a remote plasma source 740 over the substrate support 705,and a showerhead 730 between the remote plasma source 740 and thesubstrate support 705. Movable members 715 may extend from the substratesupport 705 towards the showerhead 730 to position the substrate 710.Examples of movable members can include lift pins and peripheral grips.The substrate 710 may include a metal seed layer, where the metal seedlayer includes at least one of Cu, Co, Ru, Pd, Rh, Ir, Os, Ni, Au, Ag,Al, and W. In some embodiments, the thickness of the metal seed layercan be less than about 100 Å.

In FIG. 7A, the movable members 715 in a processing chamber 750 mayposition a substrate 710 in an actuated position. The actuated positioncan place the substrate 710 at a distance A₁ closer to the showerhead730 than an unactuated position (as illustrated in FIG. 7B). In theactuated position, the distance A₁ between the substrate 710 and theshowerhead 730 can be between about 0.05 inches and about 0.75 inches. Adistance B₁ between the substrate 710 and the substrate support 705 canbe any desired distance. For example, the distance B₁ can be greaterthan about 1 inch, such as between about 1 inch and about 5 inches. Theshowerhead 730 can be maintained at a relatively cool temperature, suchas less than about 30° C.

Returning to FIG. 6A, at step 610 a, the substrate is moved towards asubstrate support in the processing chamber. In some embodiments, thesubstrate can be moved via the movable members to an unactuatedposition. The unactuated position is further from a showerhead in theprocessing chamber than the actuated position. In some embodiments, thesubstrate in the unactuated position may be in contact with thesubstrate support. For example, the movable members may be retracted sothat the substrate can rest on the substrate support. In someembodiments, a gap can exist between the substrate support and thesubstrate, and heat transfer can occur via conduction, convection,radiation, or combinations thereof. The substrate support can be heated,which in turn can heat the substrate. The substrate support may beheated to a processing temperature, such as a temperature between about0° C. and about 400° C. The temperature of the substrate support candepend on the metal seed layer of the substrate. For example, thesubstrate support can be heated between about 250° C. and about 300° C.for cobalt, and between about 75° C. and about 100° C. for copper.Higher temperatures of the substrate can speed up the metal oxidereduction reactions. However, the temperature may be selected to notexceed an agglomeration temperature of the metal seed layer. When thesubstrate is heated, the substrate may be exposed to a remote plasmatreatment.

FIG. 7B shows an example of a cross-sectional schematic diagram of aplasma treatment apparatus 700 at one of the stages of treating asubstrate with a metal seed layer (such as at step 610 a). The plasmatreatment apparatus 700 includes a substrate 710 over the substratesupport 705, where the substrate 710 is in the unactuated position. Inthe unactuated position, the substrate 710 is positioned at a distanceA₂ from the showerhead 730 and is further away from the showerhead 730than in the actuated position. The distance A₂ between the showerhead730 and the substrate 710 can be greater than about 1 inch, such asbetween about 1 inch and about 5 inches. The substrate 710 and thesubstrate support 705 can be in contact with each other, or a distanceB₂ between the substrate 710 and the substrate support 705 can berelatively small so as to allow efficient heat transfer between thesubstrate 710 and the substrate support 705. In some embodiments, thedistance B₂ can be between about 0 inches and about 0.5 inches. In someembodiments, the movable members 715 can be retracted so that thesubstrate 710 rests on the substrate support 705. The substrate support705 can position the substrate 710 relative to the showerhead 730 byvertically moving the substrate support 710. The showerhead 730 can bemaintained at a relatively cool temperature, such as less than about 30°C.

The distance A₂ can be adjusted and can tune the rate of reaction andthe uniformity of reaction during processing of the substrate. Forexample, where the substrate support 705 is closer to the showerhead730, the rate of reduction may proceed faster but achieve less uniformresults. The distance A₂ can be adjusted by vertical movement of thesubstrate support 705. In some embodiments, the substrate support 705may move from a first position to a second position in the processingchamber, where a distance between the first position and the secondposition is greater than about 1 inch. An increased degree of freedomfor positioning the substrate support 705 provides greater flexibilityin tuning the rate and uniformity of the subsequent reduction treatment.

Returning to FIG. 6A, at step 615 a, a remote plasma can be formed of areducing gas species in a remote plasma source, where the remote plasmaincludes radicals of the reducing gas species. The remote plasma can beformed by exposing the reducing gas species to a source of energy. Theenergy source can produce radicals, ions, and other charged species thatcan be flowed towards the substrate. In some embodiments, the energysource can be an RF discharge. When the remote plasma is formed, thesubstrate can be or is already heated to a desired processingtemperature. In some embodiments, a showerhead is connected to theremote plasma source and filters out the ions so that the radicals ofthe reducing gas species can be flowed towards the substrate in theprocessing chamber.

At step 620 a, the metal seed layer of the substrate is exposed to theradicals of the reducing gas species. A portion of the metal seed layercan include an oxide of the metal seed layer. Ions, radicals, and othercharged species formed in the remote plasma flow through the showerhead,and ions and other charged species can be filtered out so that thesubstrate is substantially exposed to radicals of the reducing gasspecies. The metal oxide can react with the radicals of the reducing gasspecies or the reducing gas species itself to convert the metal oxide tometal. The reaction takes place under conditions that convert the metaloxide to metal. The metal oxide in the metal seed layer is reduced toform a film integrated with the metal seed layer. Reduction of a metaloxide in a metal seed layer using a reducing gas species can bedescribed in U.S. application Ser. No. 13/787,499 (attorney docket no.LAMRP027), filed Mar. 6, 2013, which is incorporated herein by referencein its entirety and for all purposes. In some embodiments, radicals ofthe reducing gas species flow through the showerhead when the showerheadis maintained at a temperature below about 30° C.

FIG. 7C shows an example of a cross-sectional schematic diagram of aplasma treatment apparatus 700 at one of the stages of treating asubstrate with a metal seed layer (such as at steps 615 a and 620 a).The plasma treatment apparatus 700 includes a remote plasma source 740over the substrate 710 and one or more coils 744 surrounding the wallsof the remote plasma source 740. A gas inlet 742 can be connected to theremote plasma source 740 to deliver a reducing gas species 720 into aninternal volume of the remote plasma source 740. The reducing gasspecies 720 can be flowed at a flow rate between about 500 sccm andabout 30,000 sccm, which can be applicable to any substrate size. Insome embodiments, the reducing gas species 720 can include at least oneof H₂, NH₃, CO, B₂H₆, sulfite compounds, carbon and/or hydrocarbons,phosphites, and N₂H₄. Power supplied to the one or more coils 744 cangenerate a remote plasma of the reducing gas species 720 in the remoteplasma source 740. RF plasma power supplied to the coils 744 can bebetween about 0.5 kW and about 6 kW. The remote plasma can includeradicals of the reducing gas species 720, such as H*, NH*, NH₂*, orN₂H₃*. The remote plasma can also include ions and other chargedspecies, but the showerhead 730 can filter them out so that the radicalsof the reducing gas species 720 arrive at the substrate 710. Theradicals of the reducing gas species 720 flow from the remote plasmasource 740 through the showerhead 730 and onto the surface of thesubstrate 710 in the processing chamber 750. The showerhead 730 can bemaintained at a relatively cool temperature, such as less than about 30°C. The cooled showerhead 730 can limit excess heat from reaching thesubstrate 710 and avoid damaging the metal seed layer in the substrate710.

In FIG. 7C, the substrate 710 can remain in an unactuated position. Adistance A₃ between the substrate 710 and the showerhead 730 can beadjusted by moving the substrate support 705. Adjusting the distance A₃can tune the rate of reduction reaction and the uniformity of thereduction reaction occurring at the substrate 710. For example, ashorter distance A₃ can lead to faster conversion of metal oxide butless uniformity, while a longer distance A₃ can lead to slowerconversion of metal oxide but greater uniformity. In some embodiments,the distance A₃ can be the same as the distance A₂. Movable members 715can be retracted so that the substrate 710 and the substrate support 705remain in contact, or a distance B₃ between the substrate 710 and thesubstrate support 705 can be the same as the distance B₂ in FIG. 7B.

The temperature of the substrate support 705 can be adjusted via anactive heating or active cooling system. The temperature can be tunedaccording to the metal seed layer in the substrate 710 being treated.For example, the temperature of the substrate support 705 can be changedwhen switching between two different metal seed layers that requireoperating in two different temperature regimes. For example, thesubstrate support 705 can be heated between about 250° C. and about 300°C. for a cobalt seed layer, and switched to be between about 75° C. andabout 100° C. for a copper seed layer.

Returning to FIG. 6A, at step 625 a, the substrate is exposed to acooling gas. The cooling gas can include at least one of argon, helium,and nitrogen. In some embodiments, the cooling gas can be produced byexpanding a cold liquid to a gas. Exposing the substrate to the coolinggas can cool the substrate to a temperature below about 30° C. Thus, thecooling gas can be delivered at a temperature below ambient conditionsto cool the substrate. In some embodiments, the substrate can be movedto an actuated position via the movable members prior to exposing thesubstrate to the cooling gas. The substrate can be exposed to thecooling gas while in the actuated position for faster cooling. In someembodiments, the substrate can be transferred to an electroplatingapparatus after exposing the substrate to the cooling gas.Alternatively, the substrate may be transferred to an electrolessplating or other metal deposition apparatus. In some embodiments, theprocessing chamber can be vented to atmospheric conditions with aventing gas after exposing the substrate to the cooling gas.

FIG. 7D shows an example of a cross-sectional schematic diagram of aplasma treatment apparatus 700 at one of the stages of treating asubstrate with a metal seed layer (such as at step 625 a). The plasmatreatment apparatus 700 can include one or more cooling gas inlets 722for delivering a cooling gas 760. The cooling gas inlets 722 may bepositioned around the substrate 710, including above and to the side ofthe substrate 710. Cooling gas 760 can be directed onto the substrate710 through the showerhead 730 and perpendicular to the substrate plane.Cooling gas 760 can also be directed onto the substrate 710 and parallelto the substrate plane from cooling gas inlets 722 on the sides of theprocess chamber 750. The cooling gas 760 can be flowed into the processchamber 750 at a flow rate between about 0.1 slm and about 100 slm. Thecooling gas inlets 722 can flush cooling gas 760 across the substrate710 to rapidly cool the substrate 710 prior to transferring thesubstrate to an electroplating, electroless plating, or other metaldeposition apparatus. In some embodiments, the substrate 710 can becooled without turning off or cooling the substrate support 705. Thiscan enable the substrate 710 to be treated and cooled within a singleprocess chamber 750 without having to use a two-chamber design havingseparate heating and cooling zones.

In FIG. 7D, the substrate 710 can be in an actuated position. A distanceA₄ between the showerhead 730 and the substrate 710 can be between about0.05 inches and about 0.75 inches. In some embodiments, the distance A₄can be the same as the distance A₁ in FIG. 7A. By positioning thesubstrate 710 closer to a cooled showerhead 730 and away from a hotsubstrate support 705, the substrate 710 can be cooled at a faster rate.Movable members 715 can lift the substrate 710 away from the substratesupport 705 and towards the showerhead 730. A distance B₄ between thesubstrate support 705 and the substrate 710 can be greater than about 1inch, or between about 1 inch and about 5 inches. In some embodiments,the distance B₄ can be the same as the distance B₁ in FIG. 7A. In someembodiments, when the substrate 710 is in the actuated position andcooled to about room temperature, the process chamber 750 can be ventedto atmospheric conditions and transferred to an electroplating,electroless plating, or other metal deposition apparatus.

FIG. 6B shows an exemplary flow diagram illustrating another method oftreating a substrate with a metal seed layer. At step 605 b of themethod 600 b, a substrate with a metal seed layer can be provided in aprocessing chamber, as generally described at step 605 a of the method600 a. The metal seed layer can have a portion that has been convertedto oxide of the metal.

At step 610 b, a remote plasma of a reducing gas species can be formedin a remote plasma source, where the remote plasma includes one or moreof: radicals, ions, and UV radiation from the reducing gas species. Theenergy of the remote plasma may be increased to generate higher energyspecies, including higher energy ions. Higher energy ions may beproduced in high density plasma (HDP) processing systems and/orsputtering systems. The remote plasma may also generate UV radiation asa result of excitation of the reducing gas species. The generated UVradiation can have a wavelength between about 100 nm and about 400 nm.For example, the generated UV radiation can include short wavelength UVlight, such as between about 120 nm and about 200 nm, and longwavelength UV light, such as between about 200 nm and about 400 nm. Inaddition, the remote plasma may include neutrals and/or generaterecombined molecules of the reducing gas species.

At step 615 b, the metal seed layer of the substrate is exposed to theplasma, where the exposure reduces the oxide of the metal and reflowsthe metal in the metal seed layer. In some implementations, reflow ofthe metal and the reduction of the metal oxide may occur concurrently.In some implementations, the remote plasma can include radicals, ions,and UV radiation from the reducing gas species, or some combinationthereof. A showerhead between the remote plasma source and theprocessing chamber can have a thickness, a number of holes, and anaverage diameter of holes configured to permit radicals, ions, and UVradiation flow or otherwise travel through the showerhead toward thesubstrate. The radicals, ions, and UV radiation may enter the processingchamber and reduce metal oxide in the metal seed layer. High energy ionsmay penetrate further from the surface of the substrate to provide areducing chemistry throughout more of the metal seed layer. UV radiationmay activate the metal oxide surface to improve the thermodynamics ofthe reduction process, or directly reduce the metal oxide itself. The UVradiation may also be absorbed by the reducing gas species and give riseto radicals that can reduce metal oxide. Furthermore, neutral moleculesof the reducing gas species may further react and reduce metal oxide inthe metal seed layer.

In some implementations, the metal in the metal seed layer may beexcited and mobilized upon exposure. The metal may be reflowed to reducegaps and voids in the metal seed layer, which can reduce the surfaceroughness of the metal seed layer. How much the metal is reflowed candepend on the temperature of the substrate, the chamber pressure, thereducing gas species, and the intensity of the UV radiation, forexample. As the metal is reflowed and redistributed on the underlyinglayer, a more uniform and continuous metal seed layer can be formed.

EXAMPLES

The following examples illustrate the viability of using a color sensorto monitor oxide layer thickness and to gauge the effectiveness of aplasma pretreatment for reducing oxides on metal seed layers. Inparticular, the sensitivity of the b* color component to oxide layerthickness will be demonstrated.

FIG. 8 shows the results of experiments done on 6 wafers having a 200 Åoxide layer. For each wafer, labeled “W1” through “W6,” the value of theb* color component was measured before and after treatment with H₂plasma: the b* measurement on the left labeled “Pre-QSM” was taken priorto H₂ plasma treatment and the b* measurement on the right labeled“Post” was taken after an H₂ plasma treatment of the indicated duration(11 seconds, 20 seconds, and so forth). It is seen for all 6 wafers thatplasma treatment causes a significant increase in the value of the b*color component, maxing out for plasma treatment durations of 60 secondsor longer. Note that for the first wafer, labeled “W1”, an additional b*value was also measured after a “treatment” with no reducing H₂ gas inthe processing chamber. This is seen to give the same b* value as if nopretreatment had been done, providing further confirmation that oxidereduction accounts for the changed values of the b* color component. Theresults are summarized in the following table:

TABLE II Process Condition b* Change No H₂, 2 kW, 60 s Process  0.24%With H₂, 2 kW, 11 s Process  −39.8% With H₂, 2 kW, 20 s Process  −35.5%With H₂, 2 kW, 40 s Process −136.2% With H₂, 2 kW, 60 s Process −158.3%With H₂, 2 kW, 120 s Process −171.3% With H₂, 2 kW, 300 s Process−163.9%

FIGS. 9A through 9C compare the affect of H₂ plasma treatment on thevalues of each of the three color components: L*, a*, and b* (FIGS.9A-9C, respectively). In these experiments, 5 wafers having differentoxide layer thicknesses—50 Å, 100 Å, 200 Å, 400 Å, and 1000 Å—underwentpretreatment. Comparing the 3 figures, it is seen that, for all oxidelayer thicknesses, only the b* color component shows statisticallysignificant variations pre- and post-plasma treatment. It is noted thatthe difference seems to be somewhat more pronounced for the thinneroxide layers of 50 Å, 100 Å.

Whereas FIGS. 8 and 9A-9C demonstrated the sensitivity of the b* colorcomponent in a bench-top setting, FIGS. 10A, 10B, 11A, and 11Bdemonstrate the effectiveness of monitoring the b* color component inreal-time in the load-lock of a plasma treatment apparatus, such thatschematically illustrated in FIGS. 5A-5D. These FIGS. 10A-11B) show thevalue of the b* color component as a function of time over the course ofa “multilayer recipe” where the wafer passes through the outboundload-lock twice.

First referring to FIG. 10A, it is seen that the wafer's first passunder the color sensor of the outbound load-lock occurs at about 370seconds in the plot and corresponds to the wafer leaving the plasmaprocessing chamber without the plasma having been turned on—in otherwords, it represents a measurement of the b* color component beforeplasma treatment. This first peak has two shoulders on it bracketing thecenter of the peak where it has its maximum value. The reason for thisis that the pedestal in the load-lock is raised and lowered whileholding the wafer, and thus the higher values in the center of the peakcorrespond to the pedestal in the “up” position and the substrate beingcloser to the color sensor. This underscores the importance of keepingthe color sensor at an optimal distance from the surface of the wafer tomaximize the signal-to-noise ratio of the b* component.

The wafer's second pass under the color sensor of the outbound load-lockoccurs at about 610 seconds in FIG. 10A and corresponds to the waferleaving the plasma processing chamber after the plasma was turned on foroxide reduction. The plasma process had a duration of 60 seconds at atemperature of 250 C (prior to plasma treatment, the wafer had a 100 Åoxide layer). The shoulders are present in the peak at 610 seconds asseen in the previous peak at 370 seconds, but the overall magnitude ofthe b* values are significantly reduced confirming that the b* colorcomponent may serve as an indicator of plasma treatment. FIG. 10B zoomsin on these two regions (as indicated by the dashed lines in thefigures) and again emphases the differences in b* color component valuesthat one sees pre and post plasma treatment.

Once again, the shoulders on the peaks shown in FIG. 10A illustrate theimportance of choosing the right gap between the surface of thesubstrate and the head of the color sensor in order to have a strongenough b* signal and an adequate signal-to-noise ratio. Based onexperiments like the one just described it has been found that a gap ofbetween about 0.1″ and 5″ is adequate, and more preferred, between about0.4″ and 1″.

Finally, data similar to that of FIG. 10B is shown in FIGS. 11A and 11B,except, that in the latter figures, the plots show results for 6 wafers(each having a 200 Å oxide layer) which have been plasma treated fordifferent time durations. FIG. 11A shows results for 6 plasma treatments(of different time durations) at 250 C, and FIG. 11B shows results for 5plasma treatments at 75 C. For nearly all cases, a significant change inb* color component is exhibited versus that measured from each waferbefore plasma treatment (labeled “pre” in the figures). The highertemperature results in FIG. 11A (250 C) appear to (for the most part)“max out” (oxide removal saturates) at even just 11 seconds of plasmatreatment, whereas at the lower temperature shown in FIG. 11B (75 C),there is only a slight change in the b* color component at 11 seconds, asignificant change appearing first in the 30 second result, and thenbecoming more pronounced for longer time durations up to the 300 secondresult shown in the figure. In summary, the results shown in FIGS. 11Aand 11B illustrate that even at the lower temperature of 75 C, only 30seconds of plasma treatment generates a significant change in themeasured b* color component upon which an assessment of plasma treatmenteffectiveness can thus be made.

System Controllers

The plasma treatment methodologies and techniques for assessing oxidereduction effectiveness may be implemented in program instructions whichmay reside on the system controller of a plasma treatment apparatusand/or may reside on a remote non-transitory medium which is accessiblefrom and readable by the controller of the plasma treatment apparatus.An example of such a system controller is schematically illustrated inFIG. 5A. As shown in FIG. 5A, system controller 550 includes one or morememory devices 556, one or more mass storage devices 554, and one ormore processors 552. Processor 552 may include one or more CPUs, ASICs,general-purpose computer(s) and/or specific purpose computer(s), one ormore analog and/or digital input/output connection(s), one or morestepper motor controller board(s), etc.

In some embodiments, a system controller (e.g., 550 in FIG. 5A) controlssome or all of the operations of a process tool (e.g., plasma treatmentapparatus 500 in FIG. 5A) including the operations of its individualprocess stations. Machine-readable system control instructions 558 maybe provided for implementing/performing the plasma treatmentmethodologies and color sensor operation and color signal analysis asdescribed herein. The instructions may be provided on machine-readable,non-transitory media which may be coupled to and/or read by the systemcontroller. The instructions may be executed on processor 552—the systemcontrol instructions, in some embodiments, loaded into memory device 556from mass storage device 554. System control instructions may includeinstructions for controlling the timing, mixture of gaseous and liquidreactants, chamber and/or station pressures, chamber and/or stationtemperatures, wafer temperatures, target power levels, RF power levels(e.g., DC power levels, RF bias power levels), RF exposure times,substrate pedestal, chuck, and/or susceptor positions, and otherparameters of a particular process performed by a process tool.

Semiconductor substrate processing operations may employ various typesof processes including, but not limited to, processes related to theetching of film on substrates, deposition processes (such as atomiclayer deposition (ALD), by plasma-activation of surface adsorbed filmprecursors), as well as other types of substrate processing operations,such as plasma-based oxide removal from a metal seed layer inpreparation for electroplating, as well as control of electroplatingoperations.

System control instructions 558 may be configured in any suitable way.For example, various process tool component subroutines or controlobjects may be written to control operation of the process toolcomponents necessary to carry out various process tool processes. Systemcontrol instructions may be coded in any suitable computer readableprogramming language. In some embodiments, system control instructionsare implemented in software, in other embodiments, the instructions maybe implemented in hardware—for example, hard-coded as logic in an ASIC(application specific integrated circuit), or, in other embodiments,implemented as a combination of software and hardware.

In some embodiments, system control software 558 may includeinput/output control (IOC) sequencing instructions for controlling thevarious parameters described above. For example, each phase of adeposition and/or etch process or processes may include one or moreinstructions for execution by the system controller. The instructionsfor setting process conditions for a film deposition and/or etch processphase, for example, may be included in a corresponding deposition and/oretch recipe phase. In some embodiments, the recipe phases may besequentially arranged, so that all instructions for a process phase areexecuted concurrently with that process phase.

Other computer-readable instructions and/or programs stored on massstorage device 554 and/or memory device 556 associated with systemcontroller 550 may be employed in some embodiments. Examples of programsor sections of programs include a substrate positioning program, aprocess gas control program, a pressure control program, a heatercontrol program, and a plasma control program.

A substrate positioning program may include instructions for processtool components that are used to load the substrate onto pedestal and tocontrol the spacing between the substrate and other parts of processtool. The positioning program may include instructions for appropriatelymoving substrates in and out of the reaction chamber as necessary todeposit and/or etch film on the substrates.

A process gas control program may include instructions for controllinggas composition and flow rates and optionally for flowing gas into thevolumes surrounding one or more process stations prior to depositionand/or etch in order to stabilize the pressure in these volumes. In someembodiments, the process gas control program may include instructionsfor introducing certain gases into the volume(s) surrounding the one ormore process stations within a processing chamber during film depositionand/or etching operations on substrates. The process gas control programmay also include instructions to deliver these gases at the same rates,for the same durations, or at different rates and/or for differentdurations depending on the composition of the film being depositedand/or the nature of the etching process involved. The process gascontrol program may also include instructions for atomizing/vaporizing aliquid reactant in the presence of helium or some other carrier gas in aheated injection module.

A pressure control program may include instructions for controlling thepressure in the process station by regulating, for example, a throttlevalve in the exhaust system of the process station, a gas flow into theprocess station, etc. The pressure control program may includeinstructions for maintaining the same or different pressures duringdeposition of the various film types on the substrates and/or etching ofthe substrates.

A heater control program may include instructions for controlling thecurrent to a heating unit that is used to heat the substrates.Alternatively or in addition, the heater control program may controldelivery of a heat transfer gas (such as helium) to the substrate. Theheater control program may include instructions for maintaining the sameor different temperatures in the reaction chamber and/or volumessurrounding the process stations during deposition of the various filmtypes on the substrates and/or etching of the substrates.

A plasma control program may include instructions for setting RF powerlevels, frequencies, and exposure times in one or more process stationsin accordance with the embodiments herein. In some embodiments, theplasma control program may include instructions for using the same ordifferent RF power levels and/or frequencies and/or exposure timesduring film deposition on and/or etching of the substrates.

In some embodiments, there may be a user interface associated with thesystem controller. The user interface may include a display screen,graphical software displays of the apparatus and/or process conditions,and user input devices such as pointing devices, keyboards, touchscreens, microphones, etc.

In some embodiments, parameters adjusted by system controller may relateto process conditions. Non-limiting examples include process gascompositions and flow rates, temperatures (e.g., substrate holder andshowerhead temperatures), pressures, plasma conditions (such as RF biaspower levels and exposure times), etc. These parameters may be providedto the user in the form of a recipe, which may be entered utilizing theuser interface.

Signals for monitoring the processes may be provided by analog and/ordigital input connections of the system controller from various processtool sensors. The signals for controlling the processes may be output onthe analog and/or digital output connections of the process tool.Non-limiting examples of process tool sensors that may be monitoredinclude mass flow controllers (MFCs), pressure sensors (such asmanometers), temperature sensors such as thermocouples, etc.Appropriately programmed feedback and control algorithms may be usedwith data from these sensors to maintain process conditions.

The various apparatuses and methods described above may be used inconjunction with lithographic patterning tools and/or processes, forexample, for the fabrication or manufacture of semiconductor devices,displays, LEDs, photovoltaic panels and the like. Typically, though notnecessarily, such tools will be used or processes conducted togetherand/or contemporaneously in a common fabrication facility.

In some implementations, a controller is part of a system, which may bepart of the above-described examples. Such systems can comprisesemiconductor processing equipment, including a processing tool ortools, chamber or chambers, a platform or platforms for processing,and/or specific processing components (a wafer pedestal, a gas flowsystem, etc.). These systems may be integrated with electronics forcontrolling their operation before, during, and after processing of asemiconductor wafer or substrate. The electronics may be referred to asthe “controller,” which may control various components or subparts ofthe system or systems. The controller, depending on the processingrequirements and/or the type of system, may be programmed to control anyof the processes disclosed herein, including the delivery of processinggases, temperature settings (e.g., heating and/or cooling), pressuresettings, vacuum settings, power settings, radio frequency (RF)generator settings, RF matching circuit settings, frequency settings,flow rate settings, fluid delivery settings, positional and operationsettings, wafer transfers into and out of a tool and other transfertools and/or load locks connected to or interfaced with a specificsystem.

Broadly speaking, the controller may be defined as electronics havingvarious integrated circuits, logic, memory, and/or software that receiveinstructions, issue instructions, control operation, enable cleaningoperations, enable endpoint measurements, and the like. The integratedcircuits may include chips in the form of firmware that store programinstructions, digital signal processors (DSPs), chips defined asapplication specific integrated circuits (ASICs), and/or one or moremicroprocessors, or microcontrollers that execute program instructions(e.g., software). Program instructions may be instructions communicatedto the controller in the form of various individual settings (or programfiles), defining operational parameters for carrying out a particularprocess on or for a semiconductor wafer or to a system. The operationalparameters may, in some embodiments, be part of a recipe defined byprocess engineers to accomplish one or more processing steps during thefabrication of one or more layers, materials, metals, oxides, silicon,silicon dioxide, surfaces, circuits, and/or dies of a wafer.

The controller, in some implementations, may be a part of or coupled toa computer that is integrated with, coupled to the system, otherwisenetworked to the system, or a combination thereof. For example, thecontroller may be in the “cloud” or all or a part of a fab host computersystem, which can allow for remote access of the wafer processing. Thecomputer may enable remote access to the system to monitor currentprogress of fabrication operations, examine a history of pastfabrication operations, examine trends or performance metrics from aplurality of fabrication operations, to change parameters of currentprocessing, to set processing steps to follow a current processing, orto start a new process. In some examples, a remote computer (e.g. aserver) can provide process recipes to a system over a network, whichmay include a local network or the Internet. The remote computer mayinclude a user interface that enables entry or programming of parametersand/or settings, which are then communicated to the system from theremote computer. In some examples, the controller receives instructionsin the form of data, which specify parameters for each of the processingsteps to be performed during one or more operations. It should beunderstood that the parameters may be specific to the type of process tobe performed and the type of tool that the controller is configured tointerface with or control. Thus as described above, the controller maybe distributed, such as by comprising one or more discrete controllersthat are networked together and working towards a common purpose, suchas the processes and controls described herein. An example of adistributed controller for such purposes would be one or more integratedcircuits on a chamber in communication with one or more integratedcircuits located remotely (such as at the platform level or as part of aremote computer) that combine to control a process on the chamber.

Without limitation, example systems may include a plasma etch chamber ormodule (employing inductively or capacitively coupled plasmas), adeposition chamber or module, a spin-rinse chamber or module, a metalplating chamber or module, a clean chamber or module, a bevel edge etchchamber or module, a physical vapor deposition (PVD) chamber or module,a chemical vapor deposition (CVD) chamber or module, an atomic layerdeposition (ALD) chamber or module, an atomic layer etch (ALE) chamberor module, an ion implantation chamber or module, a track chamber ormodule, and any other semiconductor processing systems that may beassociated or used in the fabrication and/or manufacturing ofsemiconductor wafers.

As noted above, depending on the process step or steps to be performedby the tool, the controller might communicate with one or more of othertool circuits or modules, other tool components, cluster tools, othertool interfaces, adjacent tools, neighboring tools, tools locatedthroughout a factory, a main computer, another controller, or tools usedin material transport that bring containers of wafers to and from toollocations and/or load ports in a semiconductor manufacturing factory.

Photolithographic Patterning

The apparatuses/processes described hereinabove may be used inconjunction with lithographic patterning tools or processes, forexample, for the fabrication or manufacture of semiconductor devices,displays, LEDs, photovoltaic panels and the like. Typically, though notnecessarily, such tools/processes will be used or conducted together ina common fabrication facility. Lithographic patterning of a filmtypically comprises some or all of the following steps, each stepenabled with a number of possible tools: (1) application of photoresiston a workpiece, i.e., substrate, using a spin-on or spray-on tool; (2)curing of photoresist using a hot plate or furnace or UV curing tool;(3) exposing the photoresist to visible or UV or x-ray light with a toolsuch as a wafer stepper; (4) developing the resist so as to selectivelyremove resist and thereby pattern it using a tool such as a wet bench;(5) transferring the resist pattern into an underlying film or workpieceby using a dry or plasma-assisted etching tool; and (6) removing theresist using a tool such as an RF or microwave plasma resist stripper.

Other Embodiments

Although the foregoing disclosed processes, methods, systems, andapparatuses have been described in detail within the context of specificembodiments for the purpose of promoting clarity and understanding, itwill be apparent to one of ordinary skill in the art that there are manyalternative ways of implementing these processes, methods, systems, andapparatuses which are within the scope and spirit of this disclosure.Accordingly, the embodiments described herein are to be viewed asillustrative of the disclosed inventive concepts rather than limiting orrestrictive, and are not to be used as an impermissible basis for undulylimiting the scope of the appended Claims.

1. A method of preparing a semiconductor substrate having a metal seedlayer for a subsequent electroplating operation, the method comprising:contacting the surface of the semiconductor substrate with a plasma totreat the surface by reducing metal oxides thereon; after contactingwith the plasma, measuring a post-plasma-contact color signal from saidsurface, the color signal having one or more color components; andestimating the extent of the oxide reduction due to the plasma treatmentbased, at least in part, on comparing the post-plasma contact colorsignal to one of: one or more reference color signals and apre-plasma-contact color signal from said surface.
 2. The method ofclaim 1, wherein estimating the extent of the oxide reduction due to theplasma treatment is done based on the b* component of the post-plasmacontact color signal.
 3. The method of claim 1, wherein estimating theextent of the oxide reduction due to the plasma treatment comprises:comparing the post-plasma-contact color signal to one or more referencecolor signals.
 4. The method of claim 3, wherein the comparing is donebased on the b* component of the color signals.
 5. The method of claim1, wherein estimating the extent of the oxide reduction due to theplasma treatment comprises: calculating one or more metrics, each ofwhich is indicative of the difference between the post-plasma-contactcolor signal and a reference color signal from a set of one or morereference color signals.
 6. The method of claim 5, wherein each metricis monotonically related to the absolute value of the difference betweenthe b* component of the post-plasma-contact color signal and the b*component of a reference color signal.
 7. The method of claim 1, furthercomprising: before contacting with the plasma, measuring apre-plasma-contact color signal from said surface, the color signalhaving one or more color components; and wherein estimating the extentof the oxide reduction due to the plasma treatment comprises: comparingthe pre- and post-plasma-contact color signals.
 8. The method of claim7, wherein the comparing is done based on the b* component of the colorsignals.
 9. The method of claim 7, wherein estimating the extent of theoxide reduction due to the plasma treatment comprises: calculating ametric which is indicative of the difference between the pre- andpost-plasma-contact color signals.
 10. The method of claim 9, whereinthe metric is monotonically related to the absolute value of thedifference between the b* component of the pre- and post-plasma-contactcolor signals.
 11. The method of claim 1, wherein the plasma containshydrogen radicals.
 12. The method of claim 1, wherein the metal iscopper.
 13. The method of claim 1, wherein the metal is cobalt.
 14. Themethod of claim 1, wherein measuring the post-plasma-contact colorsignal is performed with a color sensor located about 0.1-5″ from thesubstrate surface during the measuring.
 15. The method of claim 14,wherein measuring the post-plasma-contact color signal is performed witha color sensor located about 0.4-1″ from the substrate surface duringthe measuring.
 16. A plasma treatment apparatus for reducing metaloxides present on the surface of a metal seed layer of a semiconductorsubstrate in preparation for a subsequent electroplating operation, theapparatus comprising: a processing chamber having at least oneprocessing station therein; a substrate holder configured to hold asubstrate at the processing station; a plasma generator configured togenerate a plasma within and/or provide it to the processing chamber; acolor sensor configured to measure a color signal from a substrate, thecolor signal having one or more color components; and a controllerhaving non-transitory computer-readable instructions for: operating theplasma generator to generate a plasma within and/or provide it to theprocessing chamber so that the plasma contacts the surface of asubstrate at the processing station to treat it by reducing metal oxidesthereon; operating the color sensor, after the plasma contacts thesubstrate surface, to measure a post-plasma-contact color signal fromthe surface, the color signal having one or more color components; andestimating the extent of the oxide reduction due to the plasma treatmentbased on the post-plasma contact color signal.
 17. The apparatus ofclaim 16, wherein the color sensor is located and/or configured so as tomeasure the color signal from the substrate while the substrate islocated at the processing station.
 18. The apparatus of claim 16,further comprising: a load-lock configured to provide substrate accessto the processing chamber; and wherein the color sensor is locatedand/or configured so as to measure the color signal from the substratewhile the substrate is located within the load-lock.
 19. The apparatusof claim 16, wherein the color sensor is configured to measure a colorsignal having a b* color component.
 20. The apparatus of claim 19,wherein estimating the extent of the oxide reduction due to the plasmatreatment is done based on the b* component of the post-plasma contactcolor signal.
 21. The apparatus of claim 16, wherein the plasmagenerator is remote from the processing chamber.